An Asymmetric Supercapacitor–Diode (CAPode) for Unidirectional Energy Storage

Zhang, En; Fulik, Natalia; Hao, Guang‐Ping; Zhang, Han‐Yue; Kaneko, Katsumi; Borchardt, Lars; Brunner, Eike; Kaskel, Stefan

doi:10.1002/anie.201904888

Cited by 52 publications

(55 citation statements)

References 37 publications

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“…Similar observations in recent work by Zhang et al support this interpretation and show how it can be exploited to make a supercapacitor device with diode-like properties. [104] Comparison of NMR spectra for 1 M NBu4-BF4 / acetonitrile adsorbed on small pore (0.87 nm) and large pore (4.0 nm) carbons showed that spontaneous adsorption of both NBu4 cations and BF4 anions is prevented in the small pore carbon due to the large cation size. However, the much smaller BF4 anions can be electrosorbed when the small pore carbon is positively polarised.…”

Section: Characterising Electrosorption Mechanisms In Pcmsmentioning

confidence: 99%

NMR studies of adsorption and diffusion in porous carbonaceous materials

Forse

Merlet

Grey

et al. 2021

Progress in Nuclear Magnetic Resonance Spectroscopy

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Porous carbonaceous materials have many important industrial applications including energy storage, water purification, and adsorption of volatile organic compounds. Most of their applications rely upon the adsorption of molecules or ions within the interior pore volume of the carbon particles.Understanding the behaviour and properties of adsorbate species on the molecular level is therefore key for optimising porous carbon materials, but this is very challenging owing to the complexity of the disordered carbon structure and the presence of multiple phases in the system. In recent years, NMR spectroscopy has emerged as one of the few experimental techniques that can resolve adsorbed species from those outside the pore network. Adsorbed, or "in-pore" species are shielded with respect to their free (or "ex-pore") counterparts. This shielding effect arises primarily due to ring currents in the carbon structure in the presence of a magnetic field, such that the observed chemical shift differences upon adsorption are independent of the observed nucleus to a first approximation.Theoretical modelling has played an important role in rationalising and explaining these experimental observations. Together, experiments and simulations have enabled a large amount of information to be gained on the adsorption and diffusion of adsorbed species, as well as on the structural and magnetic properties of the porous carbon adsorbent. Here, we review the methodological developments and applications of NMR spectroscopy and related modelling in this field, and provide perspectives on possible future applications and research directions.

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Section: Characterising Electrosorption Mechanisms In Pcmsmentioning

confidence: 99%

NMR studies of adsorption and diffusion in porous carbonaceous materials

Forse

Merlet

Grey

et al. 2021

Progress in Nuclear Magnetic Resonance Spectroscopy

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“…[11][12][13][14][15] The concept of a supercapacitor-diode (CAPode) was proposed by Kaskel et al in 2019, integrating the characteristics of a diode into an EDLC, and a CAPode can provide energy-storage capacity for only one charging direction. [16] The CAPode is essentially an asymmetric supercapacitor architecture comprising microporous carbon negative and mesoporous carbon positive electrodes. During charging, the large-size cations of the electrolyte are blocked outside the microporous carbon, and smallsize anions are electrosorbed into the pores of mesoporous carbon.…”

Section: Introductionmentioning

confidence: 99%

“…This phenomenon leads the CAPode to allow forward and reverse currents but to only charge in the positive direction, indicating a novel alternating current (AC) "ionic diode" analogue of semiconductor-based diodes. [16] The CAPode may present considerable potential in the simultaneous charge storage and rectification of AC circuits, [17,18] iontronics, [19,20] information storage, and logic operations. [21][22][23] Nonetheless, the CAPode concept recently emerged, and the as-built CAPode presents two shortcomings.…”

Section: Introductionmentioning

confidence: 99%

Construction of Supercapacitor‐Based Ionic Diodes with Adjustable Bias Directions by Using Poly(ionic liquid) Electrolytes

Feng

Wang

et al. 2021

Advanced Materials

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The newly emerging supercapacitor‐diode (CAPode), integrating the characteristics of a diode into an electrical‐double‐layer capacitor, can be employed to extend conventional supercapacitors to new technological applications and may play a crucial role in grid stabilization, signal propagation, and logic operations. However, the reported CAPodes have only been able to realize charge storage in the positive‐bias direction. Here, bias‐direction‐adjustable CAPodes realized by using a polycation‐based ionic liquid (IL) or a polyanion‐based IL as electrolyte in an asymmetric carbon‐based supercapacitor architecture are proposed. The resulting CAPodes exhibit charge‐storage function at only the positive‐ or negative‐bias direction with a high rectification ratio (≈80% for rectification ratio II, RRII) and an outstanding cycling life (4500 cycles), representing a crucial breakthrough for designing high‐performance capacitive ionic diodes.

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“…Precise pore size engineering may lead to selective ion‐sieving. [ 35 ] Organic electrolytes offer a much wider voltage window. [ 37 ] Ionic conductivity and transfer number are decisive factors for tailoring G‐Cap performance in future.…”

Section: Resultsmentioning

confidence: 99%

“…[ 31–34 ] As a 1st generation device in this direction we have recently reported an ion‐based supercapacitor diode (CAPode) with high rectification ratio via pore size engineering and an ion‐sieving mechanism effectively blocking the negative bias charging direction. [ 35 ]…”

Section: Introductionmentioning

confidence: 99%

Switchable Supercapacitors with Transistor‐Like Gating Characteristics (G‐Cap)

Lochmann

Bräuniger

Gottsmann

et al. 2020

Adv Funct Materials

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A novel three-electrode electrolyte supercapacitor (electric double-layer capacitor [EDLC]) architecture in which a symmetrical interdigital "working" two-electrode micro-supercapacitor array (W-Cap) is paired with a third "gate" electrode that reversibly depletes/injects electrolyte ions into the system controlling the "working" capacity effectively is described. All three electrodes are based on precursor-derived nanoporous carbons with welldefined specific surface area (735 m 2 g −1 ). The interdigitated architecture of the W-Cap is precisely manufactured using 3D printing. The W-Cap operating with a proton conducting PVA/H 2 SO 4 -hydrogel electrolyte and high capacitance (6.9 mF cm −2 ) can be repeatedly switched "on" and "off ". By applying a low DC bias potential (−0.5 V) at the gate electrode, the AC electroadsorption in the coupled interdigital nanoporous carbon electrodes of the W-Cap is effectively suppressed leading to a stark capacity drop by two orders of magnitude from an "on" to an "off " state. The switchable micro-supercapacitor is the first of its kind. This general concept is suitable for implementing a broad range of nanoporous materials and advanced electrolytes expanding its functions and applications in future. The integration of intelligent functions into EDLC devices has extensive implications for diverse areas such as capacitive energy management, microelectronics, iontronics, and neuromodulation.

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An Asymmetric Supercapacitor–Diode (CAPode) for Unidirectional Energy Storage

Cited by 52 publications

References 37 publications

NMR studies of adsorption and diffusion in porous carbonaceous materials

NMR studies of adsorption and diffusion in porous carbonaceous materials

Construction of Supercapacitor‐Based Ionic Diodes with Adjustable Bias Directions by Using Poly(ionic liquid) Electrolytes

Switchable Supercapacitors with Transistor‐Like Gating Characteristics (G‐Cap)

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